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71.
Varela-Álvarez A Sordo JA Piedra E Nebra N Cadierno V Gimeno J 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(38):10583-10599
A general mechanism to rationalize Ru(IV) -catalyzed isomerization of the C=C bond in O-allylic substrates is proposed. Calculations supporting the proposed mechanism were performed at the MPWB1K/6-311+G(d,p)+SDD level of theory. All experimental observations in different solvents (water and THF) and under different pH conditions (neutral and basic) can be interpreted in terms of the new mechanism. Theoretical analysis of the transformation from precatalyst to catalyst led to structural identification of the active species in different media. The experimentally observed induction period is related to the magnitudes of the energy barriers computed for that process. The theoretical energy profile for the catalytic cycle requires application of relatively high temperatures, as is experimentally observed. Participation of a water molecule in the reaction coordinate is mechanistically essential when the reaction is carried out in aqueous medium. The new mechanistic proposal helped to develop a new experimental procedure for isomerization of allyl ethers to 1-propenyl ethers under neutral aqueous conditions. This process is an unique example of efficient and selective catalytic isomerization of allyl ethers in aqueous medium. 相似文献
72.
Dr. Ángel J. Jiménez Michael Sekita Dr. Esmeralda Caballero Dr. M. Luisa Marcos Dr. M. Salomé Rodríguez‐Morgade Prof. Dr. Dirk M. Guldi Prof. Tomás Torres 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(43):14506-14514
In a novel electron‐donor–acceptor conjugate, phthalocyanine (Pc) and perylenediimide (PDI) are connected through a trans‐platinum(II) diacetylide linker to yield Pc‐Pt‐PDI 1 . In the ground state, the presence of PtII disrupts the electronic communication between the two electroactive components, as revealed by UV/Vis spectroscopy and electrochemical studies. The photophysical behavior of 1 is compared with that of the corresponding Pc‐PDI electron‐donor–acceptor conjugate 2 in terms of charge separation and charge recombination. The insertion of PtII between Pc and PDI impacts the results in a longer‐lived Pc . +/PDI . ? radical ion‐pair state. In addition, the intermediately formed Pc triplet excited state is formed with higher quantum yields in 1 than in 2 . 相似文献
73.
Garbiñe Álvarez Francisco Alcaide Oscar Miguel Laura Calvillo María Jesús Lázaro Jacob J. Quintana Juan Carlos Calderón Elena Pastor 《Journal of Solid State Electrochemistry》2010,14(6):1027-1034
This paper presents the behavior of ordered mesoporous carbon (OMC)-supported catalysts as anodes for direct methanol fuel
cells (DMFC), fed with an aqueous methanol solution. OMC samples were prepared by the nanocasting method from a polymerized
furan resin using mesoporous silica as a template. Pt and PtRu nanoparticles were supported on OMC with high dispersion, the
particle size being 2.4 nm at PtRu loading of 15 wt.%. The resulting catalysts were analyzed using carbon monoxide stripping
voltammetry, cyclic voltammetry, and chronoamperometry in three-electrode experiments and recording cell voltage vs. current
density curves in practical DMFC. It was found that PtRu-catalyzed technical electrodes exhibited good activity towards methanol
electrooxidation in half-cell experiments under fuel-cell-relevant conditions. Specifically, Pt85Ru15/OMC catalyst showed the highest catalytic enhancement compared to Pt/OMC for the steady-state electrooxidation of methanol
at 60 °C and 0.5 V, by a factor of 22 in 2-M MeOH solution. DMFC single cells yielded an open-circuit voltage of 0.625 V at
60 °C. Polarization curves indicate that DMFC with OMC-supported Pt85Ru15 catalyst at the anode exhibited the best performance. 相似文献
74.
Ángela Martínez‐Peragón Dr. Delia Miguel Rocío Jurado Dr. José Justicia Prof. José M. Álvarez‐Pez Dr. Juan M. Cuerva Dr. Luis Crovetto 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(2):447-455
9‐Alkyl xanthenones with different aliphatic pendant groups have been easily prepared by means of nucleophilic addition of the corresponding Grignard derivative to a tert‐butyldimethylsilyl ether (TBDMS)‐protected 3,6‐dihydroxy‐xanthenone. The photophysical behavior of the new dyes has been explored by using absorption, steady‐state‐, and time‐resolved fluorescence measurements. We determined the equilibrium constants, visible spectral characteristics, fluorescence quantum yield, and decay times. Remarkably, they retain similar fluorescent properties of fluorescein including the characteristic phosphate‐mediated excited‐state proton‐transfer (ESPT) reaction. 6‐Hydroxy‐9‐isopropyl‐3H‐xanthen‐3‐one ( 5 ) was investigated in living cells; it presented a good permeability and efficient accumulation inside the cytosol. For the first time, we reported that the requirement of an aryl group at C‐9 is no longer needed and new fluorescent sensors can be therefore easily developed. 相似文献
75.
Coordination Chemistry of Cyclopropenylidene‐Stabilized Phosphenium Cations: Synthesis and Reactivity of Pd and Pt Complexes 下载免费PDF全文
Ágnes Kozma Tobias Deden Dr. Javier Carreras Christian Wille Dr. Jekaterina Petuškova Jörg Rust Dr. Manuel Alcarazo 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(8):2208-2214
A straightforward synthesis of cyclopropenylidene‐stabilized phosphenium cations 1 a – g through the reaction of [(iPr2N)2C3+Cl]BF4 with secondary phosphines is described. Their donor ability was evaluated by analysis of the CO stretching frequency in Rh complexes [RhCl(CO)L2](BF4)2 and electrochemical methods. The cyclopropenium ring induces a phosphite‐type behavior that can be tuned by the other two substituents attached to the phosphorus atom. Despite of the positive charge that they bear, phosphenium cations 1 a – g still act as two‐electron donor ligands, forming adducts with PdII and PtII precursors. Conversely, in the presence of Pd0 species, an oxidative insertion of the Pd atom into the Ccarbene–phosphorus bond takes place, providing dimeric structures in which each Pd atom is bonded to a cyclopropenyl carbene while two dialkyl/diaryl phosphide ligands serve as bridges between the two Pd centers. The catalytic performance of the resulting library of PtII complexes was tested; all of the cationic phosphines accelerated the prototype 6‐endo‐dig cyclization of 2‐ethynyl‐1,1′‐biphenyl to afford pentahelicene. The best ligand 1 g was used in the synthesis of two natural products, chrysotoxene and epimedoicarisoside A. 相似文献
76.
Macarena Eugui Katerine Rasquin Andrés López Radcenco Leopoldo Suescun Guillermo Moyna 《Tetrahedron letters》2018,59(16):1560-1563
We describe a novel pericyclic/anionic cascade reaction on tropolonic substrates that combines a Diels-Alder reaction, an oxa-Michael addition, and an acyloin rearrangement to afford tricyclic α-hydroxy-β-methoxyketones. Spectroscopic, crystallographic, and mechanistic studies indicate that the process requires stabilization of reaction intermediates through intramolecular H-bonding to take place, and suggest that the conjugate addition step involves a catalytic cycle with initial formation of an ammonium enolate and sustained by an alkoxide ion pair. Given the rich functionality and structural complexity generated in a single step, the process could be exploited in the preparation of natural product-like compound libraries. 相似文献
77.
Physisorption and chemisorption of hydrogen on solid-state materials are two fundamentally different interactions, both of which display advantages and drawbacks for hydrogen storage. It has been hypothesised that their combination by merging two classes of materials showing different sorption behaviour towards hydrogen in the same composite may synergistically combine their desirable properties. As representatives of such composites, palladium nanoparticles, nanoclusters, and single atoms have been encapsulated in a metal-organic framework matrix, embedded, or immobilised in its pores, respectively. In this minireview, we review advances on the understanding and potential applications of the combination of Pd with metal-organic framework matrices through the analysis of the nanocomposite materials’ interaction with hydrogen and sorption properties. 相似文献
78.
D. Gómez-Vázquez L. R. Cajero-Zul J. A. Torres-Ávalos K. Sandoval-García J. A. Cortés-Ortega F. A. López-Dellamary 《高分子科学杂志,A辑:纯化学与应用化学》2019,56(5):417-428
Carbon nanotubes (CNTs) chemically functionalized were used to synthesize a series of novel nanocomposite hydrogels by in situ polymerization with acrylic acid (AA) and acrylamide (AM). A novel strategy was developed to prepare these hydrogels. CNTs were functionalized following a three-step chemical procedure: (i) purified carbon nanotubes (CNTsp) were partially surface oxidized to obtain CNTs with hydroxyl, carbonyl and carboxyl groups on their sidewalls (CNTsoxi), (ii) CNTsoxi were reacted with oxalyl chloride to obtain CNTs functionalized with acyl chloride groups (CNTsOCl), and (iii) CNTsOCl were reacted with acrylic acid (AA). The product, AA modified CNTsOCl (CNTsOCl-AA) was used to prepare the (CNTsOCl-AA-AM) nanocomposite hydrogels, where anhydride groups were tethered to the surface of the CNTsOCl-AA. The swelling process in water was evaluated as a consequence of the anhydride group hydrolysis, which broke some chemical links between CNTsOCl-AA and crosslinked AA-AM network. Equilibrium-swelling values of all hydrogels increased as the content of AA increased and were larger for AA-AM hydrogels than for CNTsOCl-AA-AM nanocomposite hydrogels. Young’s moduli of CNTsOCl-AA-AM nanocomposite hydrogels prepared with 1 or 2?wt.% AA, reached larger values than those measured for AA-AM hydrogels. This tendency was reversed when the AA content was raised to 3?wt.%. 相似文献
79.
Ákos Kuki Ghazaleh Shemirani Lajos Nagy Borbála Antal Miklós Zsuga Sándor Kéki 《Journal of the American Society for Mass Spectrometry》2013,24(7):1064-1071
A simple collision model for multiple collisions occurring in quadrupole type mass spectrometers was derived and tested with leucine enkaphalin a common mass spectrometric standard with well-characterized properties. Implementation of the collision model and Rice-Ramsperger-Kassel-Marcus (RRKM) algorithm into a spreadsheet software allowed a good fitting of the calculated data to the experimental survival yield (SY) versus collision energy curve. In addition, fitting also ensured to estimate the efficiencies of the kinetic to internal energy conversion for Leucine enkephalin in quadrupole-time-of-flight and triple quadrupole instruments. It was observed that the experimental SY versus collision energy curves for the leucine enkephalin can be described by the Rice-Ramsperger-Kassel (RRK) formalism by reducing the total degrees of freedom (DOF) to about one-fifth. Furthermore, this collision model with the RRK formalism was used to estimate the critical energy (E o ) of lithiated polyethers, including polyethylene glycol (PEG), polypropylene glycol (PPG), and polytetrahydrofurane (PTHF) with degrees of freedom similar to that of leucine enkephalin. Applying polyethers with similar DOF provided the elimination of the effect of DOF on the unimolecular reaction rate constant. The estimated value of E o for PEG showed a relatively good agreement with the value calculated by high-level quantum chemical calculations reported in the literature. Interestingly, it was also found that the E o values for the studied polyethers were similar. Figure
? 相似文献
80.
Manzano R Andrés JM Álvarez R Muruzábal MD de Lera ÁR Pedrosa R 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(21):5931-5938
A series of chiral thioureas derived from easily available diamines, prepared from α-amino acids, have been tested as catalysts in the enantioselective Michael additions of nitroalkanes to α,β-unsaturated ketones. The best results are obtained with the bifunctional catalyst prepared from L-valine. This thiourea promotes the reaction with high enantioselectivities and chemical yields for aryl/vinyl ketones, but the enantiomeric ratio for alkyl/vinyl derivatives is very modest. The addition of substituted nitromethanes led to the corresponding adducts with excellent enantioselectivity but very poor diastereoselectivity. Evidence for the isomerization of the addition products has been obtained from the reaction of chalcone with [D(3)]nitromethane, which shows that the final addition products epimerize under the reaction conditions. The epimerization explains the low diastereoselectivity observed in the formation of adducts with two adjacent tertiary stereocenters. Density functional studies of the transition structures corresponding to two alternative activation modes of the nitroalkanes and α,β-unsaturated ketones by the bifunctional organocatalyst have been carried out at the B3LYP/3-21G* level. The computations are consistent with a reaction model involving the Michael addition of the thiourea-activated nitronate to the ketone activated by the protonated amine of the organocatalyst. The enantioselectivities predicted by the computations are consistent with the experimental values obtained for aryl- and alkyl-substituted α,β-unsaturated ketones. 相似文献